System for collecting liquid samples

ABSTRACT

Systems and methods are described to determine whether a sample transmitted through a transfer line from a remote sampling system contains a suitable sample to analyze by an analysis system. A system embodiment includes, but is not limited to, a sample receiving line configured to receive a liquid segment a first detector configured to detect the liquid segment at a first location in the sample receiving line; a second detector configured to detect the liquid segment at a second location in the sample receiving line downstream from the first location; and a controller configured to register a continuous liquid segment in the sample receiving line when the first detector and the second detector match detection states prior to the controller registering a change of state of the first detector.

RELATED APPLICATIONS

The present application is a continuation under 35 U.S.C. § 120 of U.S.patent application Ser. No. 15/735,850, filed Dec. 12, 2017 (now U.S.Pat. No. 10,585,108), which is a national stage application under 35U.S.C. § 371 of PCT Application No. PCT/US16/39327, filed Jun. 24, 2016,which itself claims the benefit under 35 U.S.C. § 119(e) of U.S.Provisional Application Ser. No. 62/185,239, filed Jun. 26, 2015; U.S.Provisional Application Ser. No. 62/276,705, filed Jan. 8, 2016; andU.S. Provisional Application Ser. No. 62/277,241, filed Jan. 11, 2016.U.S. patent application Ser. No. 15/735,850; PCT Application No.PCT/US16/39327; and U.S. Provisional Application Ser. Nos. 62/185,239,62/276,705, and 62/277,241 are herein incorporated by reference in theirentireties.

BACKGROUND

In many laboratory settings, it is often necessary to analyze a largenumber of chemical or biological samples at one time. In order tostreamline such processes, the manipulation of samples has beenmechanized. Such mechanized sampling can be referred to as autosamplingand can be performed using an automated sampling device, or autosampler.

Inductively Coupled Plasma (ICP) spectrometry is an analysis techniquecommonly used for the determination of trace element concentrations andisotope ratios in liquid samples. ICP spectrometry employselectromagnetically generated partially ionized argon plasma whichreaches a temperature of approximately 7,000K. When a sample isintroduced to the plasma, the high temperature causes sample atoms tobecome ionized or emit light. Since each chemical element produces acharacteristic mass or emission spectrum, measuring the spectra of theemitted mass or light allows the determination of the elementalcomposition of the original sample.

Sample introduction systems may be employed to introduce the liquidsamples into the ICP spectrometry instrumentation (e.g., an InductivelyCoupled Plasma Mass Spectrometer (ICP/ICP-MS), an Inductively CoupledPlasma Atomic Emission Spectrometer (ICP-AES), or the like), or othersample detector or analytic instrumentation for analysis. For example, asample introduction system may withdraw an aliquot of a liquid samplefrom a container and thereafter transport the aliquot to a nebulizerthat converts the aliquot into a polydisperse aerosol suitable forionization in plasma by the ICP spectrometry instrumentation. Theaerosol is then sorted in a spray chamber to remove the larger aerosolparticles. Upon leaving the spray chamber, the aerosol is introducedinto the plasma by a plasma torch assembly of the ICP-MS or ICP-AESinstruments for analysis.

SUMMARY

Systems and methods are described to determine whether a sampletransmitted through a transfer line from a remote sampling systemcontains a suitable sample to analyze by an analysis system. A systemembodiment includes, but is not limited to, a sample receiving lineconfigured to receive a liquid segment a first detector configured todetect the liquid segment at a first location in the sample receivingline; a second detector configured to detect the liquid segment at asecond location in the sample receiving line downstream from the firstlocation; and a controller configured to register a continuous liquidsegment in the sample receiving line when the first detector and thesecond detector match detection states prior to the controllerregistering a change of state of the first detector.

This Summary is provided to introduce a selection of concepts in asimplified form that are further described below in the DetailedDescription. This Summary is not intended to identify key features oressential features of the claimed subject matter, nor is it intended tobe used as an aid in determining the scope of the claimed subjectmatter.

DRAWINGS

The Detailed Description is described with reference to the accompanyingfigures. Any dimensions included in the accompanying figures areprovided by way of example only and are not meant to limit the presentdisclosure.

FIG. 1 is a partial line diagram illustrating a system configured toanalyze samples transported over long distances in accordance withexample embodiments of the present disclosure.

FIG. 2A is an environmental view illustrating a remote sampling deviceused in a remote sampling system, in accordance with example embodimentsof the present disclosure.

FIG. 2B is an environmental view illustrating a remote sampling deviceused in a remote sampling system, in accordance with example embodimentsof the present disclosure.

FIG. 3A is an environmental view illustrating an analysis device used inan analysis system, in accordance with example embodiments of thepresent disclosure.

FIG. 3B is an environmental view illustrating an analysis device used inan analysis system, in accordance with example embodiments of thepresent disclosure.

FIG. 4 is a partial line diagram illustrating an analysis system withinthe system configured to analyze samples transported over long distancesin accordance with example embodiments of the present disclosure.

FIG. 5 is a partial line diagram illustrating a detector that can beutilized within the analysis system shown in FIG. 4 in accordance withexample embodiments of the present disclosure.

FIG. 5 is an environmental view illustrating an analysis system having aplurality of analysis devices to analyze a sample received from a remotesampling system in accordance with example embodiments of the presentdisclosure.

FIG. 7 is a diagrammatic illustration of a system including a samplereceiving line and detectors configured to determine when the samplereceiving line contains a continuous liquid segment between thedetectors in accordance with example embodiments of the presentdisclosure.

FIG. 8 is a partial cross section of a sample transfer line containingmultiple segments of a sample obtained by a remote sampling system inaccordance with example embodiments of the present disclosure.

FIG. 9 is timeline illustrating multiple liquid sample segments suppliedto a sample receiving line and registered by two detectors in accordancewith example embodiments of the present disclosure.

FIG. 10 is a flow diagram illustrating a method for determining when asample receiving line contains a continuous liquid segment betweendetectors in accordance with example embodiments of the presentdisclosure.

FIG. 11 is a process flow diagram of a control system for monitoring andcontrolling process operations based on chemical detection limits inaccordance with example embodiments of the present disclosure.

FIG. 12 is a schematic diagram of a processing facility incorporating aplurality of remote sampling systems in accordance with exampleembodiments of the present disclosure.

FIG. 13 is a chart illustrating metallic contamination of a chemicalbath over time, with data points representing manual sampling and datapoints obtained with an automatic system in accordance with exampleembodiments of the present disclosure.

DETAILED DESCRIPTION

Referring generally to FIGS. 1 through 13, example systems configured toanalyze samples transported over long distances are described. Inexample embodiments, one or more samples can be analyzed by multipleanalysis systems, where such analysis systems can comprise differinganalysis techniques. A system 100 includes an analysis system 102 at afirst location. The system 100 can also include one or more remotesampling systems 104 at a second location remote from the firstlocation. For instance, the one or more remote sampling systems 104 canbe positioned proximate a source of chemical, such as a chemical storagetank, a chemical treatment tank (e.g., a chemical bath), a chemicaltransport line or pipe, or the like (e.g., the second location), to beanalyzed by the analysis system 102, where the analysis system 102 canbe positioned remote from the remote sampling system(s) 104, such as ananalysis hub for a production facility (e.g., the first location). Thesystem 100 can also include one or more remote sampling system(s) 104 ata third location, a fourth location, and so forth, where the thirdlocation and/or the fourth location are remote from the first location.In implementations, the third location, the fourth location, and otherlocations of the remote sampling systems 104 can be remote fromrespective other locations of other remote sampling systems 104. Forexample, one remote sampling system 104 can be positioned at a waterline (e.g., a deionized water transport line), whereas one or more otherremote sampling systems 104 can be positioned at a chemical storagetank, a chemical treatment tank (e.g., a chemical bath), a chemicaltransport line or pipe, or the like. In some embodiments, the system 100also may include one or more remote sampling system(s) 104 at the firstlocation (e.g., proximate to the analysis system 102). For example, asampling system 104 at the first location may include an autosamplercoupled with the analysis system 102. The one or more sampling systems104 can be operable to receive samples from the first location, thesecond location, the third location, the fourth location, and so forth,and the system 100 can be operable to deliver the samples to theanalysis system 102 for analysis.

A remote sampling system 104 can be configured to receive a sample 150and prepare the sample 150 for delivery (e.g., to the analysis system102) and/or analysis. In embodiments, the remote sampling system 104 canbe disposed various distances from the analysis system 102 (e.g., 1 m, 5m, 10 m, 30 m, 50 m, 100 m, 300 m, 1000 m, etc.). In implementations,the remote sampling system 104 can include a remote sampling device 106and a sample preparation device 108. The sample preparation device 108may further include a valve 148, such as a flow-through valve. Inimplementations, the remote sampling device 106 can include a deviceconfigured for collecting a sample 150 from a sample stream or source(e.g., a liquid, such as waste water, rinse water, chemical, industrialchemical, etc., a gas, such as an air sample and/or contaminants thereinto be contacted with a liquid, or the like). The remote sampling device106 can include components, such as pumps, valves, tubing, sensors,etc., suitable for acquiring the sample from the sample source anddelivering the sample over the distance to the analysis system 102. Thesample preparation device 108 can include a device configured to preparea collected sample 150 from the remote sampling device 106 using adiluent 114, an internal standard 116, a carrier 154, etc., such as toprovide particular sample concentrations, spiked samples, calibrationcurves, or the like, and can rinse with a rinse solution 158.

In some embodiments, a sample 150 may be prepared (e.g., prepared sample152) for delivery and/or analysis using one or more preparationtechniques, including, but not necessarily limited to: dilution,pre-concentration, the addition of one or more calibration standards,and so forth. For example, a viscous sample 150 can be remotely diluted(e.g., by sample preparation device 108) before being delivered to theanalysis system 102 (e.g., to prevent the sample 150 from separatingduring delivery). As described herein, a sample that has beentransferred from the remote sampling system 104 can be referred to as asample 150, where sample 150 can also refer to a prepared sample 152. Insome embodiments, sample dilution may be dynamically adjusted (e.g.,automatically adjusted) to move sample(s) 150 through the system at adesired rate. For instance, diluent 114 added to a particular sample ortype of sample is increased when a sample 150 moves through the system100 too slowly (e.g., as measured by the transfer time from the secondlocation to the first location). In another example, one liter (1 L) ofseawater can be remotely pre-concentrated before delivery to theanalysis system 102. In a further example, electrostatic concentrationis used on material from an air sample to pre-concentrate possibleairborne contaminants. In some embodiments, in-line dilution and/orcalibration is automatically performed by the system 100. For instance,a sample preparation device 108 can add one or more internal standardsto a sample delivered to the analysis system 102 to calibrate theanalysis system 102.

In embodiments of the disclosure, the analysis system 102 can include asample collector 110 and/or sample detector 130 configured to collect asample 150 from a sample transfer line 144 coupled between the analysissystem 102 and one or more remote sampling systems 104. The samplecollector 110 and/or the sample detector 130 can include components,such as pumps, valves, tubing, ports, sensors, etc., to receive thesample 150 from one or more of the remote sampling systems 104 (e.g.,via one or more sample transfer lines 144). For example, where thesystem 100 includes multiple remote sampling systems 104, each remotesampling system can include a dedicated sample transfer line 144 tocouple to a separate portion of the sample collector 110 or to aseparate sample collector 110 of the analysis system 102. Additionally,the analysis system 102 may include a sampling device 160 configured tocollect a sample 150 that is local to the analysis system 102 (e.g., alocal autosampler).

The analysis system 102 also includes at least one analysis device 112configured to analyze samples to determine trace element concentrations,isotope ratios, and so forth (e.g., in liquid samples). For example, theanalysis device 112 can include ICP spectrometry instrumentationincluding, but not limited to, an Inductively Coupled Plasma MassSpectrometer (ICP/ICP-MS), an Inductively Coupled Plasma Atomic EmissionSpectrometer (ICP-AES), or the like. In embodiments, the analysis system102 includes a plurality of analysis devices 112 (i.e., more than oneanalysis device). For example, the system 100 and/or the analysis system102 can include multiple sampling loops, with each sampling loopintroducing a portion of the sample to the plurality of analysis devices112. As another example, the system 100 and/or the analysis system 102can be configured with a multiposition valve, such that a single samplecan be rapidly and serially introduced to the plurality of analysisdevices 112. For example, FIG. 6 shows one remote sampling system 104 influid communication with the analysis system 102, wherein the analysissystem 102 includes a multiposition valve 600 coupled with threeanalysis devices (shown as ICPMS 602, ion chromatograph (IC) Column 604,and Fourier transform infrared spectroscop (FTIR) 606) for analysis ofthe sample received from the remote sampling system 104. While FIG. 6shows an embodiment where the analysis system 102 includes threeanalysis devices, the analysis system 102 can include fewer (e.g., lessthan three) or more (e.g., more than three) analysis devices 112. Inembodiments, the analysis devices 112 can include, but are not limitedto, ICPMS (e.g., for trace metal determinations), ICPOES (e.g., fortrace metal determinations), ion chromatograph (e.g., for anion andcation determinations), liquid chromatograph (LC) (e.g., for organiccontaminants determinations), FTIR infrared (e.g., for chemicalcomposition and structural information determinations), particle counter(e.g., for detection of undissolved particles), moisture analyzer (e.g.,for detection of water in samples), gas chromatograph (GC) (e.g., fordetection of volatile components), or the like. In embodiments, theplurality of analysis devices 112 can be located at the same location asthe remote sampling device 104, while the system 100 can include one ormore additional analysis devices 112 located remotely from the remotesampling system 104 for additional or differing sample analysis thanthose analys(es) performed by the plurality of analysis devices 112.Alternatively or additionally, the plurality of analysis devices 112 canbe located at a different location than the remote sampling system 104.

The system 100 and/or analysis system 102 can be configured to reportanalyte concentration at a location over tune (shown further below withreference to FIG. 13). In some embodiments, the analysis device 112 maybe configured to detect one or more trace metals in a sample 150. Inother embodiments, the analysis device 112 may be configured for ionchromatography. For example, ions and/or cations can be collected in asample 150 and delivered to a chromatograph analysis device 112. Infurther embodiments, organic molecules, proteins, and so on, can becollected in samples and delivered to a high resolution time-of-flight(HR-ToF) mass spectrometer analysis device 112 (e.g., using a nebulizer156). Thus, systems as described herein can be used for variousapplications, including, but not necessarily limited to: pharmaceuticalapplications (e.g., with a central mass spectrometer analysis deviceconnected to multiple pharmaceutical reactors), waste monitoring of oneor more waste streams, semiconductor fabrication facilities, and soforth. For example, a waste stream may be continuously monitored forcontaminants and diverted to a tank when a contaminant is detected. Asanother example, one or more chemical streams can be continuouslymonitored via analysis of the samples obtained by one or more of theremote sampling systems 104 linked to the analysis system 102, whereby acontamination limit can be set for each of the chemical streams. Upondetection of a contaminant exceeding the contamination limit for aparticular stream, the system 100 can provide an alert.

The remote sampling system 104 can be configured to selectively couplewith at least one sample transfer line 144 so that the remote samplingsystem 104 is operable to be in fluid communication with the sampletransfer line 144 for supplying a continuous liquid sample segment 150to the sample transfer line 144. For example, the remote sampling system104 may be configured to collect a sample 150 and supply the sample 150to the sample transfer line 144 using, for instance, a flow-throughvalve 148, coupling the remote sampling system 104 to the sampletransfer line 144. The supply of the sample 150 to the sample transferline 144 can be referred to as a “pitch.” The sample transfer line 144can be coupled with a gas supply 146 and can be configured to transportgas from the second location (and possibly the third location, thefourth location, and so forth) to the first location. In this manner,liquid sample segments supplied by the remote sampling system 104 arecollected in a gas stream, and transported to the location of theanalysis system 102 using gas pressure sample transfer.

In some embodiments, gas in the sample transfer line 144 can include aninert gas, including, but not necessarily limited to: nitrogen gas,argon gas, and so forth. In some embodiments, the sample transfer line144 may include an unsegmented or minimally segmented tube having aninside diameter of eight-tenths of a millimeter (0.8 mm). However, aninside diameter of eight-tenths of a millimeter is provided by way ofexample only and is not meant to limit the present disclosure. In otherembodiments, the sample transfer line 144 may include an inside diametergreater than eight-tenths of a millimeter and/or an inside diameter lessthan eight-tenths of a millimeter. In some embodiments, pressure in thesample transfer line 144 can range from at least approximately four (4)bar to ten (10) bar. However, this range is provided by way of exampleonly and is not meant to limit the present disclosure. In otherembodiments, pressure in the sample transfer line 144 may be greaterthan ten bar and/or less than four bar. Further, in some specificembodiments, the pressure in the sample transfer line 144 may beadjusted so that samples 150 are dispensed in a generally upwarddirection (e.g., vertically). Such vertical orientation can facilitatetransfer of a sample collected at a location that is lower than theanalysis system 102 (e.g., where sample source(s) and remote samplingsystem(s) are located “downstairs” relative to the analysis system 102).

In some examples, the sample transfer line 144 can be coupled with aremote sampling system 104 in fluid communication with a first liquidbath (or chemical bath) and an analysis system 102 in fluidcommunication with a second liquid bath (or chemical bath). Inembodiments of the disclosure, the system 100 may include one or moreleak sensors (e.g., mounted in a trough) to prevent or minimize overflowat the first location and/or one or more remote locations (e.g., thesecond location, the third location, the fourth location, and so forth).A pump, such as a syringe pump or a vacuum pump, may be used to loadsample into the sampling, device 106. A valve 148 may be used to selectthe sample 150 at the remote sampling system 104, and the sample 150 canbe supplied to the sample transfer line 144, which can deliver thesample 150 to the analysis system 102 at the first location. Anotherpump, such as a diaphragm pump, may be used to pump a drain on theanalysis system 102 and pull the sample 150 from the sample transferline 144.

The system 100 can be implemented as an enclosed sampling system, wherethe gas and samples in the sample transfer line 144 are not exposed tothe surrounding environment. For example, a housing and/or a sheath canenclose one or more components of the system 100. In some embodiments,one or more sample lines of the remote sampling system 104 may becleaned between sample deliveries. Further, the sample transfer line 144may be cleaned (e.g., using a cleaning solution) between samples 150.

The sample transfer line 144 can be configured to selectively couplewith a sample receiving line 162 (e.g., a sample loop 164) at the firstlocation so that the sample loop 164 is operable to be in fluidcommunication with the sample transfer line 144 to receive a continuousliquid sample segment. The delivery of the continuous liquid samplesegment to the sample loop 164 can be referred to as a “catch.” Thesample loop 164 is also configured to selectively couple with theanalysis device 112 so that the sample loop 164 is operable to be influid communication with the analysis device 112 to supply thecontinuous liquid sample segment to the analysis device 112 (e.g., whenthe system 100 has determined that a sufficient liquid sample segment isavailable for analysis by the analysis system 102). In embodiments ofthe disclosure, the analysis system 102 can include one or moredetectors configured to determine that the sample loop 164 contains asufficient amount of the continuous liquid sample segment for analysisby the analysis system 102. In one example, a sufficient amount of thecontinuous liquid sample can include enough liquid sample to send to theanalysis device 112. Another example of a sufficient amount of thecontinuous liquid sample can include a continuous liquid sample in thesample receiving line 162 between a first detector 126 and a seconddetector 128 (e.g., as shown in FIG. 7). In implementations, the firstdetector 126 and/or the second detector 128 may include a light analyzer132, an optical sensor 134, a conductivity sensor 136, a metal sensor138, a conducting sensor 140, and/or a pressure sensor 142. It iscontemplated that the first detector 126 and/or the second detector 128may include other sensors. For example, the first detector 126 mayinclude a light analyzer 132 that detects when the sample 150 enters thesample loop 164, and the second detector 128 may include another lightanalyzer 132 that detects when the sample loop 164 is filled. Thisexample can be referred to as a “successful catch.” It should be notedthat the light analyzers 132 are provided by way of example only and arenot meant to limit the present disclosure. Other example detectorsinclude, but are not necessarily limited to: optical sensors,conductivity sensors, metal sensors, conducting sensors, pressuresensors, and so on.

Referring to FIG. 7, systems 100 are described that can determine when acontinuous liquid sample segment is contained in a sample receiving line162 and/or when a sample loop 164 contains a sufficient amount of thecontinuous liquid sample segment for analysis (e.g., by the analysissystem 102). In example embodiments, a first detector 126 can beconfigured to determine two or more states, which can represent thepresence of liquid (e.g., a liquid sample segment) at a first locationin the sample receiving line 162, the absence of liquid at the firstlocation in the sample receiving line 162, and so forth. For example, afirst state (e.g., represented by a first logic level, such as a highstate) can be used to represent the presence of a liquid sample segmentat the first location in the sample receiving line 162 (e.g., proximateto the first detector 126), and a second state (e.g., represented by asecond logic level, such as a low state) can be used to represent theabsence of a liquid sample segment at the first location in the samplereceiving line 162 (e.g., a void or gas in the sample receiving line162).

In some embodiments, a first detector 126 comprising a pressure sensor142 can be used to detect the presence of liquid at the first locationin the sample receiving line 162 (e.g., by detecting an increase inpressure in the sample receiving line 162 proximate to the firstlocation when liquid is present). The first detector 126 can also beused to detect the absence of liquid at the first location in the samplereceiving line 162 (e.g., by detecting a decrease in pressure in thesample receiving line 162 proximate to the first location). However, apressure sensor is provided by way of example and is not meant to limitthe present disclosure. In other embodiments, a first detector 126comprising an optical sensor 134 can be used to detect the presence ofliquid at the first location in the sample receiving line 162 (e.g., bydetecting a reduction in light passing through the sample receiving line162 proximate to the first location when liquid is present). The firstdetector 126 can also be used to detect the absence of liquid at thefirst location in the sample receiving line 162 (e.g., by detecting anincrease in light passing through the sample receiving line 162proximate to the first location). In these examples, the first detector126 can report the presence of liquid sample at the first location as ahigh state and the absence of liquid sample at the first location as alow state.

In some embodiments, a system 100 may also include one or moreadditional detectors, such as a second detector 126, a third detector,and so forth. For example, a second detector 126 can also be configuredto determine two or more states, which can represent the presence ofliquid (e.g., a liquid sample segment) at a second location in thesample receiving line 162, the absence of liquid at the second locationin the sample receiving line 162, and so forth. For example, a firststate (e.g., represented by a first logic level, such as a high state)can be used to represent the presence of a liquid sample segment at thesecond location in the sample receiving line 162 (e.g., proximate to thesecond detector 126), and a second state (e.g., represented by a secondlogic level, such as a low state) can be used to represent the absenceof a liquid sample segment at the second location in the samplereceiving line 162.

In some embodiments, a second detector 126 comprising a pressure sensor142 can be used to detect the presence of liquid at the second locationin the sample receiving line 162 (e.g., by detecting an increase inpressure in the sample receiving line 162 proximate to the secondlocation when liquid is present). The second detector 126 can also beused to detect the absence of liquid at the second location in thesample receiving line 162 (e.g., by detecting a decrease in pressure inthe sample receiving line 162 proximate to the second location).However, a pressure sensor is provided by way of example and is notmeant to limit the present disclosure. In other embodiments, a seconddetector 126 comprising an optical sensor 134 can be used to detect thepresence of liquid at the second location in the sample receiving line162 (e.g., by detecting a reduction in light passing through the samplereceiving line 162 proximate to the second location when liquid ispresent). The second detector 126 can also be used to detect the absenceof liquid at the second location in the sample receiving line 162 bydetecting an increase in light passing through the sample receiving line162 proximate to the second location). In these examples, the seconddetector 126 can report the presence of liquid sample at the secondlocation as a high state and the absence of liquid sample at the secondlocation as a low state.

A controller 118 can be communicatively coupled with one or moredetector(s) 126 and configured to register liquid at the first locationin the sample receiving line 162, the second location in the samplereceiving line 162, another location in the sample receiving line 162,and so on. For example, the controller 118 initiates a detectionoperation using a first detector 126, and liquid at the first locationin the sample receiving line 162 can be registered by the controller 118(e.g., when the controller 118 registers a change of state from low tohigh as determined by the first detector 126). Then, the first detector126 may be monitored (e.g., continuously, at least substantiallycontinuously), and the controller 118 can subsequently register anabsence of liquid at the first location in the sample receiving line 162(e.g., when the controller 118 registers a change of state from high tolow as determined by the first detector 126).

Similarly, the controller 118 can also initiate a detection operationusing a second detector 126, and liquid at the second location in thesample receiving line 162 can be registered by the controller 118 (e.g.,when the controller 118 registers a change of state from low to high asdetermined by the second detector 126). Then, the second detector 126may be monitored (e.g., continuously, at least substantiallycontinuously), and the controller 118 can subsequently register anabsence of liquid at the second location in the sample receiving line162 (e.g., when the controller 118 registers a change of state from highto low as determined by the second detector 126).

The controller 118 and/or one or more detectors 126 can include orinfluence the operation of a timer to provide timing of certain events(e.g., presence or absence of liquids at particular times at multiplelocations in the sample receiving line 162) for the system 100. As anexample, the controller 118 can monitor the times at which changes ofstate are registered by the various detector(s) in order to makedeterminations as to whether to allow the liquid sample to be directedto the analysis system 102 (e.g., as opposed to directing the liquid towaste or a holding loop). As another example, the controller 118 canmonitor the time that a liquid spends in the sample receiving line 162and/or the sample loop 164 based upon the change of states registered bythe controller 118 via the detector(s) 126.

Liquid Sample Segment Interruption & Determination of Suitable LiquidSegment

Generally, when a sample is obtained proximate an associated analysisdevice (e.g., an autosampler next to an analysis device), the sample canspan the entire distance between the sample source and the analysisdevice without requiring substantial sample amounts. However, forlong-distance transfer of a sample, filling the entire transfer line 144between with the remote sampling system 104 and the analysis system 102(e.g., up to hundreds of meters of sample length) could be prohibitiveor undesirable, such as due to environmental concerns with disposingunused sample portions, viscosity of the sample, or the like.Accordingly, in embodiments, the remote sampling system 104 does notfill the entire transfer line 144 with sample, rather, a liquid samplesegment representing a fraction of the total transfer line 144 volume issent through the transfer line 144 for analysis by the analysis system102. For example, while the transfer line 144 can be up to hundreds ofmeters long, the sample may occupy about a meter or less of the transferline 144 at any given time during transit to the analysis system 102.While sending liquid sample segments through the line can reduce theamount of sample sent from the remote sample systems 104, the sample canincur bubbles or gaps/voids in the sample transfer line 144 duringtransit to the analysis system 102. Such bubbles or gaps/voids can formdue to circumstances associated with long-distance transfer of thesample such as changes in orifices between tubing during transit, due tointeraction with residual cleaning fluid used to clean the lines betweensamples, due to reactions with residual fluid in the lines, due topressure differential(s) along the span of transfer line, or the like.For example, as shown in FIG. 8, a liquid sample 800 can be sent fromthe remote sampling system 104 through the transfer line 144 to thefirst location where the analysis system 102 is located. The volume ofthe total sample obtained by the remote sampling system 104 isrepresented by V_(TOT) in FIG. 8. As shown, gaps or voids 802 can formin the transfer line 144 during transit from the remote sampling system104. The gaps or voids 802 partition a number of sample segments 804that do not contain sufficient amounts or volume of sample for analysisby the analysis system 102. Such sample segments 804 can precede and/orfollow a larger sample segment 806 having a volume (shown as V_(SAMPLE))sufficient for analysis by the analysis system 102. In embodiments, thequantity of sample collected by the remote sampling system 104 (e.g.,V_(TOT)) is adjusted to provide a sufficient amount of sample 150 foranalysis by the analysis device 112. For instance, the volumetric ratioof the amount of sample 150 “pitched” to the amount of sample 150“caught” (e.g., V_(TOT)/V_(SAMPLE)) is at least approximately one andone-quarter (1.25). However, this ratio is provided by way of exampleonly and is not meant to limit the present disclosure. In someembodiments the ratio is greater than one and one-quarter, and in otherembodiments the ratio is less than one and one-quarter. In one example,two and one-half milliliters (2.5 mL) of sample 150 (e.g., concentratedsulfuric acid or nitric acid) is pitched, and one milliliter (1 mL) ofsample 150 is caught. In another example, one and one-half milliliters(1.5 mL) of sample 150 is pitched, and one milliliter (1 mL) of sample150 is caught. In embodiments of the disclosure, the amount of sample150 “pitched” is adjusted to account for the distance between the firstlocation and the second location, the amount of sample transfer linetubing between the first location and the second location, the pressurein the sample transfer line 144, and so forth. In general, the ratio ofV_(TOT)/V_(SAMPLE) can be greater than one to account for the formationof the gaps/voids 802 and sample segments 804 in the sample transferline 144 during transfer.

The system 100 can select which of a plurality of remote samplingsystems 104 should transmit its respective sample to the analysis system102 (e.g., “pitch”), whereby the detectors 126 facilitate determinationof whether sufficient sample is present (e.g., V_(SAMPLE) in the sampleloop 164) to send to the analysis system 102 (e.g., “catch”), or whethera void or gap is present in the line (e.g., between the detectors 126),such that the sample should not be sent to the analysis system 102 atthat particular time. If bubbles or gaps were to be present (e.g., inthe sample loop 164), their presence could compromise the accuracy ofthe analysis of the sample, particularly if the sample were to bediluted or further diluted at the analysis system 102 prior tointroduction to the analysis device 112, since the analysis device 112could analyze a “blank” solution.

In some embodiments, a system 100 can be configured to determine when acontinuous liquid sample segment (e.g., sample segment 806) is containedin a sample receiving line 162 and/or a sample loop 164, such that thesystem 100 can avoid transferring a gap or void 802 or smaller samplesegment 804 to the analysis device 112. For example, the system 100 caninclude a first detector 126 at a first location along the samplereceiving line 162 and a second detector 126 at a second location alongthe sample receiving line 162 (e.g., downstream from the firstlocation). The system 100 may also include a sample loop 164 between thefirst detector 126 and the second detector 126. In embodiments, a valve,such as a multi-port valve switchable between at least two flow pathconfigurations (e.g., a first flow path configuration of valve 148 shownin FIG. 3A; a second flow path configuration of valve 148 shown in FIG.3B, etc.), can be positioned between the first detector 126 and thesample loop 164 and between the second detector 126 and the sample loop164. In embodiments of the disclosure, the system 100 can determine thata continuous liquid sample segment is contained in the sample receivingline 162 and/or the sample loop 164 by registering liquid at both thefirst location and the second location at the same time, while notregistering a change of state from high to low via the first detector126 at the first location. Stated another way, the liquid sample hastransferred from the first detector 126 to the second detector 126continuously, with no change in state detected by the first detector 126until the second detector 126 recognizes the presence of the liquidsample.

In an example implementation in which two or more detectors are used todetermine when a sample receiving line contains a continuous liquidsegment between the detectors, a liquid segment is received in a samplereceiving line. For example, with reference to FIG. 7, sample receivingline 162 receives a liquid sample segment. Then, the liquid segment isregistered at a first location in the sample receiving line byinitiating a detection operation using a first detector configured todetect a presence and/or an absence of the liquid segment at the firstlocation in the sample receiving line. For example, with reference toFIG. 7, the first detector 126 detects a liquid sample segment at thefirst location in the sample receiving line 162 as a change of statefrom low to high. With reference to FIG. 9, liquid sample segments canbe detected at the first location at times t₁ and t₅. Then, subsequentto registering the liquid segment at the first location, the firstdetector is monitored. For instance, with reference to FIG. 7, the firstdetector 126 is monitored by the controller 118, and the first detector126 detects an absence of the liquid sample segment at the firstlocation in the sample receiving line 162 as a change of state from highto low. With reference to FIG. 9, the first location is monitored (e.g.,continuously, at least substantially continuously) beginning at times t₁and t₅, and an absence of the liquid sample segments can be detected atthe first location at times t₃ and t₆.

Similarly, the liquid segment is registered at a second location in thesample receiving line by initiating a detection operation using a seconddetector configured to detect a presence and/or an absence of the liquidsegment at the second location in the sample receiving line. Forinstance, with reference to FIG. 7, the second detector 126 detects aliquid sample segment at the second location in the sample receivingline 162 as a change of state from tow to high. With reference to FIG.9, liquid sample segments can be detected at the second location attimes t₂ and t₇. Then, subsequent to registering the liquid segment atthe second location, the second detector is monitored. For instance,with reference to FIG. 7, the second detector 126 is monitored by thecontroller 118, and the second detector 126 detects an absence of theliquid sample segment at the second location in the sample receivingline 162 as a change of state from high to low. With reference to FIG.9, the second location is monitored (e.g., continuously, at leastsubstantially continuously) beginning at times t₂ and t₇, and an absenceof the liquid sample segments can be detected at the second location attimes t₄ and t₈.

When liquid is registered at both the first location and the secondlocation at the same time, a continuous liquid segment is registered inthe sample receiving line between the first detector and the seconddetector. For instance, with reference to FIG. 7, when a high staterepresents the presence of a liquid sample segment at each of the firstdetector 126 and the second detector 126, the controller 118 registers acontinuous liquid sample segment in the sample receiving line 162 (e.g.,as present between the first detector 126 and the second detector 126).With reference to FIG. 9, a continuous liquid sample segment can beregistered at time t₂ when a liquid sample segment is detected at thesecond location.

In some embodiments, a logical AND operation can be used to determinewhen a continuous liquid segment is registered in the sample receivingline and initiate transfer of the continuous liquid segment from thesample receiving line to analysis equipment. For instance, withreference to FIG. 7, the controller 118 can use a logical AND operationon a high state at each of the first detector 126 and the seconddetector 126 and initiate a selective coupling of the sample loop 164with the analysis device 112 using the valve 148 so that the sample loop164 is operable to be in fluid communication with the analysis device112 to supply the continuous liquid sample segment to the analysisdevice 112. In some embodiments, the controller 118 may only determinewhether to switch the valve 148 to supply a continuous liquid samplesegment to the analysis device 112 when a state change from low to highis registered at the first detector 126 or the second detector 126. Insome embodiments, the system 100 requires that the high state at thesecond detector 126 is maintained for a period of time (e.g., t_(Δ)shown in FIG. 9) prior to initiating selective coupling of the sampleloop 164 with the analysis device. For example, a timer or timingfunctionality of the controller 118 and/or processor 120 can verify theperiod of time that the second detector 126 has maintained the highstate, whereby once the second detector 126 has maintained the highstate for time t_(Δ) (e.g., a threshold time) and where the firstdetector is in the high state, the controller 118 can determine that asufficient liquid sample segment (e.g., segment 806 in FIG. 8) has beencaught, and can switch the valve 148 to supply the continuous liquidsample segment to the analysis device 112. The duration of t_(Δ) cancorrespond to a time period beyond which it is unlikely for the seconddetector to be measuring a void or bubble, which can vary depending onflow rate of the sample or other transfer conditions.

In some embodiments, the controller 118 can monitor the timing of thefirst detector 126 at the high state and/or at the low state. Forexample, in embodiments where the flow characteristics of the samplebeing transferred from the remote sampling system 104 are known, thefirst detector 126 can be monitored to determine the length of timespent in the high state to approximate whether sufficient liquid samplewould be present in the sample receiving line 162 and/or the sample loop164 to cause the controller 118 to send the sample to the analysisdevice 112, either with or without confirmation of a high state at thesecond detector 126. For example, for a given flow rate of the sample,the volume of the sample can be approximated by monitoring, the lengthof time that the first detector 126 has been in the high state. However,the flow rate of a sample may not be readily apparent due tofluctuations in pump functionality, type of sample transferred,viscosity of sample, duration of transfer, distance of transfer, ambienttemperature conditions, transfer line 144 temperature conditions, or thelike, so the functionality of the second detector 126 can beinformative.

In embodiments of the disclosure, the systems and techniques describedherein can be used to determine that a portion of a sample receivingline (e.g., a sample loop) between the first detector 126 and the seconddetector 126 is filled without the presence of bubbles. For example, theabsence of liquid sample at the first location between times t₃ and t₅as described with reference to FIG. 9 may correspond to the presence ofa bubble in the sample receiving line 162. When the system 100 hasreached a condition where no bubbles would be present in the samplereceiving line 162, the controller 118 switches the valve 148 to allowthe fluid in the sample loop 164 to pass to the analysis device 112 (foranalysis or sample conditioning prior to analysis).

Example Method

FIG. 10 depicts a procedure 810 in an example implementation in whichtwo detectors are used to determine when a sample receiving linecontains a sufficient amount of sample in a continuous liquid samplesegment for analysis by an analysis system, with no gaps or voids in thecontinuous liquid sample segment. As shown, a liquid segment is receivedin a sample receiving line (Block 812). For example, the samplereceiving line 162 can receive the sample obtained by the remotesampling system 104 and transferred through transit line 144. Theprocedure 810 also includes registering the liquid segment at a firstlocation in the sample receiving line with a first detector configuredto detect the presence and/or absence of the liquid segment as ittravels past the first location (Block 814). For example, the firstdetector 126 can measure the presence of the liquid sample segment atthe first location in the sample receiving line 162. With reference toFIG. 9, liquid sample segments are detected at the first location attimes t₁ and t₅.

Next, subsequent to registering the liquid segment at the firstlocation, the first detector is monitored (Block 816). For instance, thefirst detector 126 can be monitored by the controller 118 to determinewhether there is an absence of the liquid segment at the first locationin the sample receiving line 162 (e.g., whether the first detector 126has transitioned from a high state, indicating detection of samplefluid, to a low state, wherein no sample fluid is detected). Withreference to FIG. 9, the first location is monitored (e.g.,continuously, at least substantially continuously) beginning at times t₁and t₅. Then, a continuous liquid segment is registered in the samplereceiving line when an absence of the liquid segment at the firstlocation in the sample receiving line is not registered beforeregistering the liquid segment at a second location in the samplereceiving line downstream from the first location by performing adetection operation using a second detector configured to detect apresence and/or an absence of the liquid segment at the second location(Block 818). For example, with reference to FIG. 9, the first detector126 detects the presence of the sample fluid at times t₁ and t₅, whereasthe second detector 126 detects the presence of the sample fluid attimes t₂ and t₇. Only the liquid sample segment between times t₁ and t₃at the first detector would be registered by the second detector(beginning at time t₂) without the first detector 126 detecting anabsence in the interim time before the second detector detected thatsample segment. At such time, the controller 118 could directed thevalve 148 to switch to send the sample contained in the sample loop 164to the analysis device 112. While the first detector 126 registers thepresence of the liquid sample at t₅, the first detector also detects theabsence of the liquid sample at t₆, before the second detector 126subsequently detects the presence of the liquid sample at t₇. As such,the system 100 will recognize that a gap or void (e.g., gap/void 802) ispresent in the sample loop 164 and will not switch the valve 148 foranalysis, instead allowing the inadequate sample segment (e.g., liquidsegment 804) to pass to waste. As described herein, a timer (e.g.,implemented by the controller 118) can be used to cause the valve 148 toswitch once the second detector 126 has maintained the high state for acertain period of time (e.g., t_(Δ)) after the first detector 126 hasmaintained the high state in the interim.

Control Systems

A system 100, including some or all of its components, can operate undercomputer control. For example, a processor 120 can be included with orin a system 100 to control the components and functions of systemsdescribed herein using software, firmware, hardware (e.g., fixed logiccircuitry), manual processing, or a combination thereof. The terms“controller,” “functionality,” “service,” and “logic” as used hereingenerally represent software, firmware, hardware, or a combination ofsoftware, firmware, or hardware in conjunction with controlling thesystems. In the case of a software implementation, the module,functionality, or logic represents program code that performs specifiedtasks when executed on a processor (e.g., central processing unit (CPU)or CPUs). The program code can be stored in one or morecomputer-readable memory devices (e.g., internal memory and/or one ormore tangible media), and so on. The structures, functions, approaches,and techniques described herein can be implemented on a variety ofcommercial computing platforms having a variety of processors.

For instance, one or more components of the system such as the analysissystem 102, remote sampling system 104, valves 148, pumps, and/ordetectors (e.g., the first detector 126, the second detector 126, thesample detector 130) can be coupled with a controller for controllingthe collection, delivery, and/or analysis of samples 150. For example,the controller 118 can be configured to switch a valve 148 coupling thesample loop 164 to the analysis system 102 and direct a sample 150 fromthe sample loop 164 to the analysis system 102 when a successful “catch”is indicated by the first detector 126 and the second detector 126(e.g., when both sensors detect liquid). Furthermore, the controller 118can implement functionality to determine an “unsuccessful catch” (e.g.,when the sample loop 164 is not filled with enough of a sample 150 for acomplete analysis by the analysis system 102). In some embodiments, an“unsuccessful catch” is determined based upon, for instance, variationsin the signal intensity of a signal received from a sensor, such as thefirst detector 126 or the second detector 126. In other embodiments, an“unsuccessful catch” is determined when the first detector 126 hasindicated a sample 150 in the sample receiving line 162 and apredetermined amount of time had passed in which the second detector 126has not indicated a sample 150 in the sample receiving line 162.

In some embodiments, the controller 118 is communicatively coupled withan indicator at a remote location, such as the second location, andprovides an indication (e.g., an alert) at the second location wheninsufficient sample 150 is received at the first location. Theindication can be used to initiate (e.g., automatically) additionalsample collection and delivery. In some embodiments, the indicatorprovides an alert to an operator (e.g., via one or more indicatorlights, via a display readout, a combination thereof, etc.). Further,the indication can be timed and/or initiated based upon a one or morepredetermined conditions (e.g., only when multiple samples have beenmissed). In some embodiments, an indicator can also be activated basedupon conditions measured at a remote sampling site. For instance, adetector 130 at the second location can be used to determine when sample150 is being provided to a remote sampling system 104, and the indicatorcan be activated when sample 150 is not being collected.

In some embodiments, the controller 118 is operable to provide differenttiming for the collection of samples from different remote locations,and/or for different types of samples 150. For example, the controller118 can be alerted when a remote sampling system 104 is ready to delivera sample 150 to the sample transfer line 144, and can initiate transferof the sample 150 into the sample transfer line 144. The controller 118can also be communicatively coupled with one or more remote samplingsystems 102 to receive (and possibly log/record) identifying informationassociated with samples 150, and/or to control the order that samples150 are delivered within the system 100. For example, the controller 118can remotely queue multiple samples 150 and coordinate their deliverythrough one or more of the sample transfer lines 144. In this manner,delivery of samples 150 can be coordinated along multiple simultaneousflow paths (e.g., through multiple sample transfer lines 144), one ormore samples 150 can be in transfer while one or more additional samples150 are being taken, and so on. For example, FIG. 11 shows an examplecontrol flow diagram for system 100, where the analysis system 102 isshown in fluid communication with two remote sample locations, shown assample location 900 and sample location 902, via two remote samplingsystems 104 a and 104 b and associated transfer lines 144 a and 144 b.In the embodiment shown, the analysis system 102 sends commands to eachof the remote sampling system 104 a and the remote sampling system 104b, shown as 904 a and 904 b, respectively. The remote sampling system104 a and the remote sampling system 104 b each transfer the sampleobtained at the respective sampling location (sampling location 900 forremote sampling system 104 a, sampling location 902 for remote samplingsystem 104 b) to the analysis system 102 via transfer line 144 a andtransfer line 144 b, respectively. The analysis system 102 thenprocesses the samples to determine amounts of various chemical speciescontainer therein. The analysis system 102 then determines whether anyof the amounts of the chemical species exceeds an element-specific limit(e.g., a limit for a specific contaminant in the sample). Inembodiments, the system 100 can set contamination limits independentlyfor each sampling location and for particular chemical species at eachsampling location independently. For example, the tolerance for aparticular metal contaminant may decrease during processing, sodownstream chemical samples may have lower limits for the particularchemical species than for chemical samples taken upstream. As shown inFIG. 11, the analysis system 102 determined that no chemical speciesexceeds any of the element-specific limits for the sample obtained atsampling location 900 by the remote sampling system 104 a. The analysissystem 102 then sends a CIM Host 906 an indication, shown as 908 a, topermit continuation of process applications at the sampling location 900due to operation of the process applications below the element-specificlimits. The analysis system 102 has determined that at least one of thechemical species present in the sample obtained at sampling location 902by the remote sampling system 104 b exceeds the element-specific limit(e.g., a limit for a contaminant in the sample). The analysis system 102then sends the CIM Host 906 an indication, shown as 908 b, to send analert directed to the process applications at the sampling location 902due to operation of the process applications above the element-specificlimits. The CIM Host 906 then directs, via a stop process command 910,the processes at the sampling location 902 to stop operation based uponthe analysis of the sample obtained by the remote sampling system 104 bat the sampling location 902. In embodiments, communication between theCIM Host 906 and the components of the system 100 can be facilitated bythe SECS/GEM protocol. In embodiments, the system 100 can includecontext-specific actions when an element is determined to be above anelement-specific limit in a sample for a particular sample location,where such context-specific actions can include, but are not limited to,ignoring an alert and continuing the process operation, stopping theprocess operation, running a system calibration and then re-running theover-limit sample, or the like. For example, upon a first alert, theanalysis system 102 can perform a calibration (or another calibration)and then re-run the sample, whereas a subsequent alert (e.g., a secondalert) would cause the CIM Host 906 to command the processes at theoffending sampling location to halt operations.

The controller 118 can include a processor 120, a memory 122, and acommunications interface 124. The processor 120 provides processingfunctionality for the controller 118 and can include any number ofprocessors, micro-controllers, or other processing systems, and residentor external memory for storing data and other information accessed orgenerated by the controller 118. The processor 120 can execute one ormore software programs that implement techniques described herein. Theprocessor 120 is not limited by the materials from which it is formed orthe processing mechanisms employed therein and, as such, can beimplemented via semiconductor(s) and/or transistors (e.g., usingelectronic integrated circuit (IC) components), and so forth.

The memory 122 is an example of tangible computer-readable storagemedium that provides storage functionality to store various dataassociated with operation of the controller 118, such as softwareprograms and/or code segments, or other data to instruct the processor120, and possibly other components of the controller 118, to perform thefunctionality described herein. Thus, the memory 122 can store data,such as a program of instructions for operating the system 100(including its components), and so forth. It should be noted that whilea single memory is described, a wide variety of types and combinationsof memory (e.g., tangible, non-transitory memory) can be employed. Thememory 122 can be integral with the processor 120, can comprisestand-alone memory, or can be a combination of both.

The memory 122 can include, but is not necessarily limited to: removableand non-removable memory components, such as random-access memory (RAM),read-only memory (ROM), flash memory (e.g., a secure digital (SD) memorycard, a mini-SD memory card, and/or a micro-SD memory card), magneticmemory, optical memory, universal serial bus (USB) memory devices, harddisk memory, external memory, and so forth. In implementations, thesystem 100 and/or the memory 122 can include removable integratedcircuit card (ICC) memory, such as memory 122 provided by a subscriberidentity module (SIM) card, a universal subscriber identity module(USIM) card, a universal integrated circuit card (UICC), and so on.

The communications interface 124 is operatively configured tocommunicate with components of the system. For example, thecommunications interface 124 can be configured to transmit data forstorage in the system 100, retrieve data from storage in the system 100,and so forth. The communications interface 124 is also communicativelycoupled with the processor 120 to facilitate data transfer betweencomponents of the system 100 and the processor 120 (e.g., forcommunicating inputs to the processor 120 received from a devicecommunicatively coupled with the controller 118). It should be notedthat while the communications interface 124 is described as a componentof a controller 118, one or more components of the communicationsinterface 124 can be implemented as external components communicativelycoupled to the system 100 via a wired and/or wireless connection. Thesystem 100 can also comprise and/or connect to one or more input/output(I/O) devices (e.g., via the communications interface 124), including,but not necessarily limited to: a display, a mouse, a touchpad, akeyboard, and so on.

The communications interface 124 and/or the processor 120 can beconfigured to communicate with a variety of different networks,including, but not necessarily limited to: a wide-area cellulartelephone network, such as a 3G cellular network, a 4G cellular network,or a global system for mobile communications (GSM) network; a wirelesscomputer communications network, such as a Wi-Fi network (e.g., awireless local area network (WLAN) operated using IEEE 802.11 networkstandards); an internet; the Internet; a wide area network (WAN); alocal area network (LAN); a personal area network (PAN) (e.g., awireless personal area network (WPAN) operated using IEEE 802.15 networkstandards); a public telephone network; an extranet; an intranet; and soon. However, this list is provided by way of example only and is notmeant to limit the present disclosure. Further, the communicationsinterface 124 can be configured to communicate with a single network ormultiple networks across different access points.

Example 1—Example Monitoring System

Generally, the systems 100 described herein can incorporate any numberof remote sampling systems 104 to take samples from any number ofsampling locations. In an implementation, shown in FIG. 12, the system100 includes five remote sampling systems 104 (shown as 104A, 104B,104C, 104D, 104E) positioned at five different locations of a processfacility utilizing chemical baths, bulk chemicals, environmentaleffluents, and other liquid samples. The remote sampling systems 104acquire samples at the different locations to transfer to the analysissystem 102 positioned remotely from each of the five remote samplingsystems 104. A first remote sampling system 104A is positioned proximatea deionized water pipeline 1000 and spaced from the analysis system 102by a distance (shown as d₅) of approximately forty meters (40 m). Asecond remote sampling system 104B is positioned proximate adistribution valve point 1002 and spaced from the analysis system 102 bya distance (shown as d₄) of approximately eighty meters (80 m). A thirdremote sampling system 104C is positioned proximate a chemical supplytank 1004 and spaced from the analysis system 102 by a distance (shownas d₃) of approximately eighty meters (80 m). The chemical supply tank1004 is positioned remotely from, and supplied with chemical from, achemical storage tank 1008. A fourth remote sampling system 104D ispositioned proximate a chemical supply tank 1006 and spaced from theanalysis system 102 by a distance (shown as d₂) of approximately eightymeters (80 m). The chemical supply tank 1006 is positioned remotelyfrom, and supplied with chemical from, the chemical storage tank 1008. Afifth remote sampling system 104E is positioned proximate the chemicalstorage tank 1004 and spaced from the analysis system 102 by a distance(shown as d₁) of approximately three hundred meters (300 m). While fiveremote sampling systems 104 are shown, the system 100 can utilize morethan five remote sampling systems 104 to monitor ultra-trace impuritiesthroughout the processing facility, such as at other process streams,chemical baths, bulk chemical storage, environmental effluents, andother liquid samples. In an implementation, the transfer of sample fromthe remote sampling systems 104 to the analysis system is provided at arate of approximately 1.2 meters per second (1.2 m/s), providing nearreal-time analysis (e.g., ICPMS analysis) of the ultra-trace impuritiesthroughout the processing facility.

Example 2—Reproducibility

In an implementation, the analysis system 102 was positioned one hundredmeters (100 m) from a remote sampling system 104. The remote samplingsystem 104 obtained twenty discrete samples and transported them to theanalysis system 102 for determination of the signal intensity of eachchemical specie present in each of the twenty discrete samples. Eachdiscrete sample included the following chemical species: Lithium (Li),Beryllium (Be), Boron (B), Sodium (Na), Magnesium (Mg), Aluminum (Al),Calcium (Ca), Manganese (Mn), Iron (Fe), Cobalt (Co), Nickel (Ni),Copper (Cu), Zinc (Zn), Germanium (Ge), Strontium (Sr), Silver (Ag),Cadmium (Cd), Indium (In), Tin (Sn), Antimony (Sb), Barium (Ba), Cerium(Cc), Hafnium (Hf), Tungsten (W), and Lead (Pb). Upon analysis by theanalysis system 102, it was determined that the relative standarddeviation (RSD) was less than three percent (<3%) across all twentydiscrete samples for all chemical species. Accordingly, the examplesystem 100 at one hundred meters between the analysis system 102 and theremote sampling system 104 provided reliable reproducibility fromobtaining the sample, transferring the sample one hundred meters to theanalysis system 102 (e.g., via transfer line 144) and analyzing thesamples with the analysis system 102.

Example 3—Comparison with Manual Sampling—Semiconductor Process Example

Referring to FIG. 13, a chart showing metallic contamination of achemical bath for semiconductor manufacturing processes (SC-1 bath) overtime is provided. The chart includes a portion 1100 showing data pointsfor metallic contamination measured from manual samples taken at threepoints in time. The chart also includes a portion 1102 showing the datapoints for metallic contamination measured from manual samples fromportion 1100 superimposed on data points for metallic contaminationmeasured from samples taken from the system 100 (e.g., from the remotesampling systems 104) at a sampling frequency exceeding that of themanual sampling method (e.g., at least sixteen to seventeen times morefrequently). As shown in portion 1102, a gradual increase incontaminants occurs over time in the semiconductor manufacturingprocess. Life time or life counts methods of determining when toexchange the chemicals in a particular semiconductor process (e.g., themanual sampling technique from portion 1100) are often unable to accountfor the particularities of the metallic contamination over time. Assuch, the chemicals are often exchanged without knowledge of the metalcontaminants in the bath. This can result in over-exchanging, where thechemical bath could actually provide additional wafer processing but ischanged out anyway (e.g., resulting in loss of process uptime), or inunder-exchanging, where the chemical bath actually has an unacceptablemetallic contamination but is not changed out until a later time (e.g.,potentially jeopardizing the wafers produced by the process). As can beseen in portion 1102, the metallic contamination can be tracked with thesystem 100 at a higher frequency automatically. A contamination limit1104 is set to alert the CIM Host 906 when the contaminant limit isreached for the chemical bath. The system 100 can thereforeautomatically cause a stop in process operations when the contaminationlimit 1104 is reached (e.g., avoiding under-exchanging), while allowingthe process to continue when the contamination limit 1104 is notreached, thereby providing process uptime when feasible (e.g., avoidingover-exchanging).

Conclusion

In implementations, a variety of analytical devices can make use of thestructures, techniques, approaches, and so on described herein. Thus,although systems are described herein, a variety of analyticalinstruments may make use of the described techniques, approaches,structures, and so on. These devices may be configured with limitedfunctionality (e.g., thin devices) or with robust functionality (e.g.,thick devices). Thus, a device's functionality may relate to thedevice's software or hardware resources, e.g., processing power, memory(e.g., data storage capability), analytical ability, and so on.

Generally, any of the functions described herein can be implementedusing hardware (e.g., fixed logic circuitry such as integratedcircuits), software, firmware, manual processing, or a combinationthereof. Thus, the blocks discussed in the above disclosure generallyrepresent hardware (e.g., fixed logic circuitry such as integratedcircuits), software, firmware, or a combination thereof. In the instanceof a hardware configuration, the various blocks discussed in the abovedisclosure may be implemented as integrated circuits along with otherfunctionality. Such integrated circuits may include all of the functionsof a given block, system, or circuit, or a portion of the functions ofthe block, system, or circuit. Further, elements of the blocks, systems,or circuits may be implemented across multiple integrated circuits. Suchintegrated circuits may comprise various integrated circuits, including,but not necessarily limited to: a monolithic integrated circuit, a flipchip integrated circuit, a multichip module integrated circuit, and/or amixed signal integrated circuit. In the instance of a softwareimplementation, the various blocks discussed in the above disclosurerepresent executable instructions (e.g., program code) that performspecified tasks when executed on a processor. These executableinstructions can be stored in one or more tangible computer readablemedia. In some such instances, the entire system, block, or circuit maybe implemented using its software or firmware equivalent. In otherinstances, one part of a given system, block, or circuit may beimplemented in software or firmware, while other parts are implementedin hardware.

Although the subject matter has been described in language specific tostructural features and/or process operations, it is to be understoodthat the subject matter defined in the appended claims is notnecessarily limited to the specific features or acts described above.Rather, the specific features and acts described above are disclosed asexample forms of implementing the claims.

What is claimed is:
 1. A system comprising: a sample receiving lineconfigured to receive a liquid segment; a valve communicatively coupledwith the sample receiving line, the valve configured to selectablydirect the liquid segment for analysis system or pass the liquid segmentto waste; a first detector configured to detect at least one of apresence or an absence of the liquid segment at a first location in thesample receiving line, the first detector configured to register theabsence of the liquid segment at the first location in the samplereceiving line as a first state, and register the presence of the liquidsegment at the first location in the sample receiving line as a secondstate; a second detector configured to detect at least one of a presenceor an absence of the liquid segment at a second location in the samplereceiving line downstream from the first location, the second detectorconfigured to register the absence of the liquid segment at the secondlocation in the sample receiving line as a first state, and register thepresence of the liquid segment at the second location in the samplereceiving line as a second state; and a controller communicativelycoupled with the first detector and the second detector, the controllerconfigured to register a void in the liquid segment in the samplereceiving line when the first detector is in the second state and thesecond detector is at the second state prior to the controllerregistering a change of state of the first detector from the secondstate to the first state, the controller configured to direct the liquidsegment through the valve to pass to waste when the controller registersthe void and to control the valve to direct the liquid segment foranalysis when the controller does not register the void.
 2. The systemof claim 1, wherein the sample receiving line includes a sample loop. 3.The system of claim 1, further comprising a timer configured to monitora time at which the second detector maintains the second state, whereinthe controller is configured to register the continuous liquid segmentin the sample receiving line when each of (i) the first detector is inthe second state and the second detector is at the second state prior tothe controller registering a change of state of the first detector fromthe second state to the first state and (ii) the time at which thesecond detector maintains the second state exceeds a threshold time. 4.The system of claim 1, wherein the valve is coupled between the firstlocation in the sample receiving line and the second location in thesample receiving line, the valve switchable between at least two flowpath configurations.
 5. The system of claim 4, wherein the controller isconfigured to switch the valve between the at least two flow pathconfigurations responsive to registering the continuous liquid segmentin the sample receiving line.
 6. The system of claim 1, furthercomprising: an analysis system at a third location; a remote samplingsystem at a fourth location remote from the third location, the remotesampling system configured to receive the liquid segment for analysis; asample transfer line configured to transport the liquid segment from thefourth location to the third location, the sample transfer line coupledwith the remote sampling system so that the remote sampling system isoperable to be in fluid communication with the sample transfer line fordriving the liquid segment to the third location, wherein the analysissystem includes the sample receiving line, and the sample receiving lineis configured to selectively couple with the sample transfer line andthe analysis system so that the sample receiving line is operable to bein fluid communication with the sample transfer line to receive theliquid segment and in fluid communication with the analysis system tosupply the liquid segment to the analysis system.
 7. The system of claim6, wherein the sample transfer line is at least five meters in length.8. The system of claim 6, wherein the sample transfer line is at leastten meters in length.
 9. The system of claim 6, wherein the analysissystem includes a plurality of analysis devices.
 10. The system of claim9, wherein the plurality of analysis devices includes at least two of amass spectrometer, an optical emission spectrometer, an ionchromatograph, a liquid chromatograph, a Fourier transform infraredspectrometer, a particle counter, a moisture analyzer, and a gaschromatograph.
 11. A method comprising receiving a liquid segment in asample receiving line, the sample receiving line communicatively couplewith a valve, the valve configured to selectably direct the liquidsegment for analysis system or pass the liquid segment to waste;registering a first state with a first detector responsive to detectionof the liquid segment at a first location in the sample receiving linewith the first detector, the first state of the first detectorcorresponding to a presence of the liquid segment at the first location;registering a first state with a second detector responsive to detectionof the liquid segment at a second location in the sample receiving linedownstream from the first location, the first state of the seconddetector corresponding to a presence of the liquid segment at the secondlocation; monitoring whether the second detector registered the firststate prior to the first detector registering a second state, the secondstate corresponding to a void in the liquid segment at the firstlocation; and automatically switching the valve to direct the liquidsegment through the valve to pass to waste when the void is registeredin the liquid segment and to control the valve to direct the liquidsegment for analysis when no void is registered in the liquid segment.12. The method of claim 11, wherein further comprising: determiningwhether the liquid segment includes a chemical component that exceeds anelement-specific contamination limit.
 13. The method of claim 11,further comprising: automatically sending an alert to an origin locationof the liquid segment when the continuous liquid segment is determinedto include the chemical component that exceeds the element-specificcontamination limit.
 14. The method of claim 11, wherein registering aliquid segment with no voids in the sample receiving line when thesecond detector registered the first state prior to the first detectorregistering a second state includes: registering a continuous liquidsegment in the sample receiving line when each of (i) the seconddetector registered the first state prior to the first detectorregistering a second state and (ii) the time at which the seconddetector maintains the second state exceeds a threshold time.